Process for Purifying (Hydro)Fluoroalkenes

ABSTRACT

The invention relates to a process for removing one or more undesired (hydro)halocarbon compounds from a (hydro)fluoroalkene, the process comprising contacting a composition comprising the (hydro)fluoroalkene and one or more undesired (hydro)halocarbon compounds with an aluminium-containing absorbent, activated carbon, or a mixture thereof.

RELATED APPLICATIONS

This present application is a continuation of co-pending U.S. patentapplication Ser. No. 13/502,278, filed 16 Apr. 2012, which is the U.S.National Phase entry under 35 U.S.C. §371 of International PatentApplication No. PCT/GB2010/001879, filed 8 Oct. 2010, and claims thebenefit of Great Britain Patent Application No. 0918069.6, filed 15 Oct.2009.

BACKGROUND OF THE INVENTION

The invention relates to a process for purifying (hydro)fluoroalkenes.

The listing or discussion of background information or an apparentlyprior-published document in this specification should not necessarily betaken as an acknowledgement that the information or document is part ofthe state of the art or is common general knowledge.

SUMMARY OF THE INVENTION

(Hydro)fluoroalkenes are increasingly being considered as working fluidsin applications such as refrigeration, heat pumping, foam blowing, fireextinguishers/retardants, propellants and solvency (e.g. plasma cleaningand etching). The processes used to make (hydro)fluoroalkenes can leadto the generation of toxic and/or otherwise undesirable by-products. Thepresence of small quantities of impurities may not be detrimental to thebulk physical properties of the (hydro)fluoroalkene product and for someapplications their removal is unnecessary. However, some applicationsrequire very low levels of impurities, and many of these are difficultto remove from the (hydro)fluoroalkenes by recognized means.

For instance, impurities are often removed from (hydro)fluoroalkenes bydistillation, but this method of removal is made difficult if theboiling point of the impurity is close to that of the(hydro)fluoroalkene or if substance interactions bring otherwisedissimilar boiling compounds close together (for example azeotropes).Furthermore, even after distillation, it is possible that smallquantities of undesirable impurities will remain.

3,3,3-trifluoropropene (R-1243zf) is an example of a(hydro)fluoroalkene. R-1243zf is believed to find use in applicationssuch as refrigeration. Commercially available R-1243zf contains manyimpurities, including the highly toxic species1,2,3,3,3-pentafluoropropene (R-1225ye), 1,1,3,3,3-pentafluoropropene(R-1225zc), and the chlorofluorocarbon species chlorofluoromethane(R-31), chlorofluoroethene (R-1131), trichlorofluoromethane (R-11),dichlorodifluoromethane (R-12), chlorotrifluoromethane (R-13), anddichlorotetrafluoroethane (R-114) that are damaging to the environment.Distillation is of limited use in purifying R-1243zf because it isdifficult to remove all the impurities using this technique. Forexample, R-1225zc (boiling point −25.82° C.) is very difficult to removefrom R-1243zf (boiling point −25.19° C.) by distillation.

In summary, there is a need for an improved method for purifying(hydro)fluoroalkenes.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The inventors have surprisingly found that an aluminium-containingabsorbent, activated carbon, or a mixture thereof, is effective atremoving one or more undesired (hydro)halocarbon compounds from acomposition also containing a desired (hydro)fluoroalkene.

Thus, the subject invention addresses the foregoing and otherdeficiencies by providing a process for removing one or more undesired(hydro)halocarbon compounds from a (hydro)fluoroalkene, the processcomprising contacting a composition comprising the (hydro)fluoroalkeneand one or more undesired (hydro)halocarbon compounds with analuminium-containing absorbent, activated carbon, or a mixture thereof.

By term “(hydro)fluoroalkenes”, we are referring to straight-chain orbranched unsaturated compounds that contain fluorine and optionallyhydrogen atoms in addition to carbon atoms. Thus, the term includesperfluoroalkenes as well as hydrofluoroalkenes which contain bothfluorine and hydrogen atoms in addition to carbon. Hydrofluoroalkenesare a preferred group of (hydro)fluoroalkenes. Preferred examples of(hydro)fluoroalkenes include C2-10 (hydro)fluoroalkenes, andparticularly C3-7 (hydro)fluoroalkenes. In one embodiment, the(hydro)fluoroalkene is a C3-7 hydrofluoroalkene which contains hydrogenand fluorine substituents.

In a preferred embodiment, the (hydro)fluoroalkene is a(hydro)fluoropropene. Examples of (hydro)fluoropropenes which may bepurified by the process of the invention include those containingcontain 0, 1, 2, 3, 4 or 5 hydrogen substituents and 1, 2, 3, 4, 5 or 6fluorine substituents. Preferred (hydro)fluoropropenes arehydrofluoropropenes having from 3 to 5 fluorine atoms (and thus from 1to 3 hydrogen atoms). In other words, preferred hydrofluoropropenes aretrifluoropropenes, tetrafluoropropenes and pentafluoropropenes,particularly trifluoropropenes and tetrafluoropropenes.

Examples of suitable trifluoropropenes include but are not limited to3,3,3-trifluoropropene (CF3CH═CH2, also known as R-1243zf),2,3,3-trifluoropropene (CF2HCF═CH2), 1,2,3-trifluoropropene (CFH2CF═CHF)and 1,3,3-trifluoropropene (CF2HCH═CHF). A preferred trifluoropropenewhich can be purified by the process of the invention is R-1243zf.

Examples of suitable tetrafluoropropenes include2,3,3,3-tetrafluoropropene (CF3CF═CH2, also known as R-1234yf),1,3,3,3-tetrafluoropropene (E/Z—HFC═CHCF3, also known as R-1234ze),1,2,3,3-tetrafluoropropene (HFC═CFCF2H), 1,1,3,3-tetrafluoropropene(F2C═CHCF2H) and 1,1,2,3-tetrafluoropropene (F2C═CFCH2F). R-1234ze andR-1234yf are preferred tetrafluoropropenes that can be purified by theprocess of the invention, particularly R-1234ze.

Examples of suitable pentafluoropropenes include1,2,3,3,3-pentafluoropropene (E/Z—HFC═CFCF3, also known as R-1225ye),1,1,3,3,3-pentafluoropropene (F2C═CHCF3, also known as R-1225zc) and1,1,2,3,3-pentafluoropropene (F2C═CFCF2H). Of these, R-1225ye is apreferred pentafluoropropene which can be purified by the process of theinvention.

In one embodiment, the (hydro)fluoroalkene which may be purified by theprocess of the invention is a hydrofluoropropene selected from R-1243zf,R-1234yf, R-1234ze, R-1225ye and mixtures thereof. Preferably, the(hydro)fluoroalkene is selected from R-1243zf, R-1234yf, R-1234ze andmixtures thereof, such as selected from R-1243zf and/or R-1234yf, orselected from R-1243zf and/or R-1234ze.

By the term “undesired (hydro)halocarbon compounds”, we mean anysaturated or unsaturated straight-chain or branched compounds containinghalogen and optionally hydrogen atoms in addition to carbon atoms thatit is desirable to remove from the (hydro)fluoroalkene which is beingpurified. Thus, the term includes perhalocarbons as well ashydrohalocarbons which contain both hydrogen and halogen atoms inaddition to carbon atoms. Typically, this includes (hydro)fluoroalkanes,(hydro)fluoroalkenes (hydro)fluoroalkynes and (hydro)chlorofluorocarbon(CFC) species such as (hydro)chlorofluoroalkanes,(hydro)chlorofluoroalkenes, and (hydro)chlorofluoroalkynes.

The undesired (hydro)halocarbon compounds described above can include(hydro)fluoroalkenes. The skilled person would understand that certainundesired (hydro)fluoroalkenes can be present in a compositioncontaining a desired (hydro)fluoroalkene. Examples of such undesired(hydro)fluoroalkenes may include those containing a ═CHF or ═CF2 group.The inventors have unexpectedly found that an aluminium-containingabsorbent, activated carbon, or a mixture thereof, can be effective atremoving (hydro)fluoroalkenes containing a═CHF or ═CF2 moiety(especially ═CF2) from a composition containing a desired(hydro)fluoroalkene.

By way of example, if the skilled person is attempting to purify aparticular trifluoropropene (e.g. R-1243zf), that trifluoropropene maybe contaminated by other (hydro)fluoroalkenes, such astetrafluoropropenes or pentafluoropropenes. As noted above, R-1225ye andR-1225zc are typical impurities in commercially available R-1243zf. Byuse of an aluminium-containing absorbent and/or activated carbon, suchundesired (hydro)fluoroalkenes may be removed from a compositioncontaining a desired (hydro)fluoroalkene by the process of theinvention. Accordingly, in one embodiment, the desired(hydro)fluoroalkene (e.g. (hydro)fluoropropene) that is purified by theprocess of the invention is not (i) a pentafluoropropene, such asR-1225ye, R-1225zc, or F2C═CFCF2H (e.g. R-1225zc); or (ii) a(hydro)fluoroalkene containing a ═CF2 moiety.

In one aspect, the process of the invention is effective at removing theundesired (hydro)halocarbon(s) R-1225zc, R-31, and/or R133a from acomposition comprising the desired (hydro)fluoroalkene R-1243zf.

Alternatively or additionally, the process of the invention is effectiveat removing the undesired (hydro)halocarbon trifluoromethylacetylene(TFMA) from a composition comprising the desired (hydro)fluoroalkeneR-1234ze.

Either the aluminium-containing absorbent or activated carbon may beporous or non-porous, but preferably porous.

A preferred aluminium-containing adsorbent for use in processesaccording to the invention is an alumina or alumina-containingsubstrate. Advantageously, the substrate is porous. Further informationon the various crystalline forms of alumina can be found in Acta.Cryst., 1991, B47, 617, the contents of which are hereby incorporated byreference.

Preferred aluminium-containing adsorbents (e.g. alumina) for useaccording to the invention will have functionality that facilitatestheir combination with the compounds the adsorbent is removing. Examplesof such functionality include acidity or basicity, which can beLewis-type or Bronsted-type in nature, which will facilitate itscombination with the compounds the adsorbent is removing. The acidity orbasicity can be modified in a manner well known to those skilled in theart by using modifiers such as sodium sulphate. Examples ofaluminium-containing adsorbents with acidic or basic functionalityinclude Eta-alumina, which is acidic, and Alumina AL0104, which isbasic.

Aluminosilicate molecular sieves (zeolites) are a further preferredgroup of aluminium-containing adsorbent that may be used in the subjectinvention. Typically, the zeolites have pores having openings which aresufficiently large to allow the desired and undesired compounds to enterinto the interior of the zeolite whereby the undesired compounds areretained. Accordingly, zeolites having pores which have openings whichhave a size across their largest dimension in the range of 3 Å to 12 Åare preferred.

Preferred zeolites have a pore opening sufficiently large to allow theundesired compounds to enter into the interior of the zeolite wherebythe undesired compounds are retained, whilst excluding the desiredcompound from entering the interior of the zeolite. Such zeolitestypically have openings which have a size across their largest dimensionin the range of 3 Å to 12 Å, preferably from 3 Å to 10 Å or 4 Å to 12 Å.Particularly preferred are those molecular sieves having pores whichhave openings having a size across their largest dimension in the rangeof 4 Å to 10 Å, such as 4 Å to 8 Å (e.g. 4 Å to 5 Å) and may includezeolite Y, ultra-stable Y (dealuminated-Y), zeolite beta, zeolite X,zeolite A and zeolite ZSM-5, AW-500.

By opening in this context we are referring to the mouth of the pore bywhich the undesired compound enters the body of the pore, where it maybe retained. The openings to the pores may be elliptically shaped,essentially circular or even irregularly shaped, but will generally beelliptically shaped or essentially circular. When the pore openings areessentially circular, they should have a diameter in the range of about3 Å across their smaller dimension. They can still be effective atadsorbing compounds provided that the size of the openings across theirlargest dimension is in the range of from about 3 Å to about 12 Å. Wherethe adsorbent has pores having elliptically shaped openings, which arebelow 3 Å across their smaller dimension, they can still be effective atadsorbing compounds provided that the size of the openings across theirlargest dimension is in the range of from about 3 Å to about 12 Å.

By “activated carbon”, we include any carbon with a relatively highsurface area such as from about 50 to about 3000 m2 or from about 100 toabout 2000 m2 (e.g. from about 200 to about 1500 m2 or about 300 toabout 1000 m2). The activated carbon may be derived from anycarbonaceous material, such as coal (e.g. charcoal), nutshells (e.g.coconut) and wood. Any form of activated carbon may be used, such aspowdered, granulated, extruded and pelleted activated carbon.

Activated carbon is preferred which has been modified (e.g. impregnated)by additives which modify the functionality of the activated carbon andfacilitate its combination with the compounds it is desired to removed.Examples of suitable additives include metals or metal compounds, andbases.

Typical metals include transition, alkali or alkaline earth metals, orsalts thereof. Examples of suitable metals include Na, K, Cr, Mn, Au,Fe, Cu, Zn, Sn, Ta, Ti, Sb, Al, Co, Ni, Mo, Ru, Rh, Pd and/or Pt and/ora compound (e.g. a halide, hydroxide, carbonate) of one or more of thesemetals. Alkali metal (e.g. Na or K) salts are currently a preferredgroup of additive for the activated carbon, such as halide, hydroxide orcarbonate salts of alkali metals salts. Hydroxide or carbonate salts ofalkali metals salts are bases. Any other suitable bases can be used,including amides (e.g. sodium amide).

The impregnated activated carbon can be prepared by any means known inthe art, for example soaking the carbon in a solution of the desiredsalt or salts and evaporating the solvent.

Examples of suitable commercially available activated carbons includethose available from Chemviron Carbon, such as Carbon 207C, Carbon ST1X,Carbon 209M and Carbon 207EA. Carbon ST1X is currently preferred.However, any activated carbon may be used with the invention, providedthey are treated and used as described herein.

Advantageously, a combination of an aluminium-containing absorbent andactivated carbon is used in the process of the invention, particularlywhen each are separately effective at removing particular undesiredcompounds from a composition also containing a desired(hydro)fluoroalkene. Examples of preferred combinations ofaluminium-containing absorbent and activated carbon include zeolite andactivated carbon and aluminium-containing absorbent and impregnatedactivated carbon.

The invention may be applied to any composition containing a(hydro)fluoroalkene from which it is desired to remove one or moreundesired (hydro)halocarbon compounds. For example, the composition maybe a product stream from a process for producing the(hydro)fluoroalkene. Accordingly, the process of the invention may be apurification step in a process for producing the (hydro)fluoroalkene.

The process of the invention may be one of several purification steps ina process for producing the fluoroalkene. For example, the process ofthe invention may be combined with one or more distillation,condensation or phase separation steps and/or by scrubbing with water oraqueous base.

The process of the invention requires the composition (e.g. productstream) to be in the liquid or vapour phase. Liquid phase contacting ispreferred.

Processing with a stationary bed of the adsorbent will typically beapplied to continuous processes. The composition (e.g. product stream)is passed over or through the stationary bed comprising thealuminium-containing absorbent, activated carbon, or a mixture thereof.

The aluminium-containing absorbent, activated carbon, or a mixturethereof is normally pre-treated prior to use by heating in a dry gasstream, such as dry air or dry nitrogen. This process has the effect ofactivating the aluminium-containing absorbent, activated carbon, or amixture thereof. Typical temperatures for the pre-treatment are in therange of from about 100 to about 400° C. (e.g. about 100 to about 300°C.).

The process of the invention can be operated in a batch or continuousmanner, although a continuous manner is preferred. In either case,during operation of the process, the absorption capability of thealuminium-containing absorbent, activated carbon, or a mixture thereofis gradually reduced as the pores become occupied with the one or moreundesired (hydro)halocarbon compounds. Eventually, the ability of thealuminium-containing absorbent, activated carbon, or a mixture thereofto absorb the undesired compound(s) will be substantially impaired, atwhich stage it should be regenerated. Regeneration is typically effectedby heating the used aluminium-containing absorbent, activated carbon, ora mixture thereof in a dry gas stream, such as dry air or dry nitrogen,at a temperature in the range of from about 100 to about 400° C., suchas from about 100 to about 300° C. (e.g. about 100 to about 200° C.),and a pressure in the range of from about 1 to about 30 bar (e.g. about5 to about 15 bar).

The process of the invention typically is conducted at a temperature inthe range of from about −50° C. to about 200° C., preferably from about0° C. to about 100° C., such as from about 10 to about 50° C. Thistemperature range applies to the temperature of the interior of thepurification vessel.

(Hydro)fluoroalkenes contain a double bond which is susceptible toreaction, particularly when contacted with aluminium-containingabsorbent and/or activated carbon containing reactive functionality(e.g. acid, base, metal etc). For example, certain (hydro)fluoroalkenesare known to be monomers, and one might expect them to polymerise in thepresence of such absorbents.

The inventors have found that the (hydro)fluoroalkenes are surprisinglystable in the presence of aluminium-containing absorbent and/oractivated carbon. This may be in part due to the mild conditions (e.g.temperature) under which the process of the invention can be carriedout.

Typical operating pressures for the process of the invention are fromabout 1 to about 30 bar, such as from about 1 to about 20 bar,preferably from about 5 to about 15 bar.

In the (batch) process of the invention, the aluminium-containingabsorbent, activated carbon, or a mixture thereof typically is used inan amount of from about 0.1 to about 100% by weight, such as from about1 or 5 to about 50% by weight, preferably from about 10 to about 50% byweight, based on the weight of the composition comprising the(hydro)fluoroalkene and one or more undesired compounds.

In a continuous process of the invention, the typical feed rate of thecomposition (e.g. product stream) comprising the (hydro)fluoroalkene andone or more undesired compounds to the aluminium-containing absorbent,activated carbon, or a mixture thereof is such that in the liquid phasethe contact time of the adsorbate with the adsorbent is from about 0.1to 24 hours, preferably from about 1 to 8 hours. In a preferred mode ofoperation the adsorbate is continuously recycled through the adsorbentbed until the level of the undesired components has reducedsufficiently. Where vapour phase contacting is utilised, the contacttime of the adsorbate with the adsorbent is from about 0.001 to 4 hours,preferably from about to 0.01 to 0.5 hours. In a preferred mode ofoperation the adsorbate is continuously recycled through the adsorbentbed until the level of the undesired components has reducedsufficiently.

The invention is particularly suitable for removing relatively lowlevels of undesired (hydro)halocarbon compound(s) from the composition(e.g. product stream) containing the (hydro)fluoroalkene being purified.Typical levels are from about 0.1 to about 1000 ppm, such as from about0.1 to about 500 ppm, preferably from about 1 to about 100 ppm.

The process of the invention removes at least a portion of undesired(hydro)halocarbon compound(s) present in the composition comprising thedesired (hydro)fluoroalkene. Preferably, the invention removes at least50%, 60%, 70% or 80% of the undesired compound(s) present in thecomposition comprising the desired (hydro)fluoroalkene. More preferably,the composition removes at least 90%, 95% or even 99% of the undesiredcompound(s) present in the composition comprising the desired(hydro)fluoroalkene.

Following purification by the process of the invention, the level ofundesired compound(s) in the composition comprising the desired(hydro)fluoroalkene typically will be from not detectable (by currentlyavailable techniques, such as capillary gas chromatography) to about 10ppm, such as from about 0.01 ppm to about 5 ppm, preferably from notdetectable to about 1 ppm.

The invention is illustrated by the following non-limiting examples.

Example 1

A range of adsorbents were screened for their efficacy in removing thetarget compounds R-1225zc and trifluoromethylacetylene (TFMA) fromR-1243zf. A sample of R-1243zf doped with 400 ppm wt/wt TFMA and 765 ppmwt/wt R-1225zc was prepared. 50 g of this R-1243zf was then treated with5 g of adsorbent in a sealed pressure tube at ambient temperature.Samples were taken for analysis by capillary GC after 20 minutes and insome cases after 16 hours of contacting of the R-1243zf with theadsorbent. The following adsorbents were screened:

Eta-Alumina ex-BASF—an acidic form of activated alumina

Chemviron Activated Carbon 207EA

10% Potassium hydroxide on Chemviron Activated Carbon 207EA10% Potassium carbonate on Chemviron Activated Carbon 207EA

10% Potassium Iodide on Chemviron Activated Carbon 207EA 10% PotassiumHydroxide and 10% Potassium Iodide on Chemviron Activated Carbon 207EA

Chemviron ST1x—an activated carbon comprising 207EA impregnated withvarious species including base(s)

The doped samples of 207EA were prepared by aqueous impregnation. Thedopant(s) (Ig) was/were dissolved in 100 g water and 10 g of 207EAadded. After mixing the water was removed in vacuo to leave a freerunning solid.

Prior to use all adsorbents were pre-activated at 250-300OC in anitrogen purged oven for a minimum of 16 hours.

The results are presented in the Table below:

% Removal of contaminant (0% = no effect; 100% = complete removal 20mins 20 mins 16 hrs 16 hrs Adsorbent R-1225zc TFMA R-1225zc TFMA 207EACarbon & 69 8 97 8 10% KOH 207EA Carbon & 41 4 58 29 10% K2CO3 207EACarbon & 4 7 — — 10% KI 207EA Carbon 4 −1 — — ST1x 46 9 100 31Impregnated Carbon 207EA Carbon & 13 5 70 8 10% KOH & KI Eta Alumina 7 718 16

All of the adsorbents screened showed utility in removal of either orboth of R-1225zc and TFMA from R-1243zf. However, the most effectiveadsorbents were those doped with base, either potassium hydroxide orcarbonate, including the ST1x carbon.

Example 2

A sample of commercially available R-1243zf (this may be obtained fromApollo Scientific, for example) was obtained and analysed by capillaryGC-MS. This R-1243zf was found to contain, amongst other, the followingimpurities:

PPM Boiling point Impurity wt/wt OC R-134a 2.5 −26.074 R-1225zc 7.4−25.82 R-1234yf 26 −29.69 R-134 87 −23.15 Z-R-1225ye 0.8 −19.3 R-152a251 −24.023 R-40 0.9 −24.15 R-31 11 −9.15 R-133a 2.3 +7.51

R-1225zc, R-31 and R-133a are toxic compounds and it was considereddesirable to remove them from the R-1243zf prior to use, for example asa refrigerant. Even where boiling point differences make the separationof some of these components from R-1243zf by distillation practicable,the low levels mean that such a process would be very energy intensiveand inefficient. Therefore, an alternative means of removing theseimpurities, particularly the R-1225zc, R-31 and R-133a, from 1243zf wassought. To that end a series of experiments were performed in which theefficacy of a range of adsorbent materials for the removal of the threetarget compounds R-1225zc, R-31 and R-133a from R-1243zf was tested.

The range of adsorbents screened comprised:

Eta-Alumina ex-BASF—an acidic form of activated aluminaChemviron Activated Carbon 207c—derived from coconut shells

Chemviron Activated Carbon 209M Chemviron Activated Carbon 207EA

Chemviron ST1x—an activated carbon comprising 207EA impregnated withvarious species including base(s)

Chemviron Activated Carbon 209m

13X Molecular sieve—An aluminosilicate or ZeoliteAW500—An acid stable aluminosilicate or ZeoliteAlumina AL0104—ex BASF—a basic form of alumina

The carbon based adsorbents were pre-activated at 200° C. in flowingnitrogen for 16 hours prior to use and the inorganic adsorbentsactivated at 300° C. in flowing nitrogen again for 16 hours. Theefficacy of each of the adsorbents was then assessed by treating c.a.100 g of R-1243zf with 2-4 g of each adsorbent in a re-circulatorysystem whereby the R-1243zf was continuously pumped through theadsorbent bed for 16 hours at ambient temperature. After the treatmentperiod a small sample of the R-1243zf was taken for analysis bycapillary GC-MS. The analysis of the treated R-1243zf is compared withthe untreated R-1243zf (see previous table for the amounts ofimpurities) in the following table.

Z-R- Mass Mass R-134a R-1225zc R-1234yf R-134 1225ye R-152a R-40 R-31R-133a Adsorbent R-1243zf (ppm (ppm (ppm (ppm (ppm (ppm (ppm (ppm (ppmAdsorbent (g) (g) wt/wt) wt/wt) wt/wt) wt/wt) wt/wt) wt/wt) wt/wt)wt/wt) wt/wt) Eta-Alumina 2.0000 100 96 4.2 26 85 1 141 11 4.8 3 Carbon207C 2.2879 92 3.6 7.9 28 93 1 231 4 11 1 Carbon ST1X 2.5165 109.3 3.1ND 26 87 0.5 241 5.9 4.1 ND Carbon 209M 2.6644 122.9 4.1 5.8 26 87 1 2512.97 11 1.2 13-X Sieve 3.9841 132 3.9 8 27 12 0.8 116 ND 2.4 1 AW 5003.8865 131.2 3.7 8.2 28 5 1.1 19 1 ND ND BASF AL0104 4.3562 134.6 3.2 ND25 85 0.8 236 0.9 8 ND Carbon 207 2.6738 118.1 2.4 6.8 25 84 0.8 222 1.111 2.2 EA

All of the adsorbents tested were effective in reducing the level of atleast one contaminant. However, for the three target compounds R-1225zc,R-31 and R-133a, the base impregnated activated carbon ST1x andmolecular sieve AW500 were particularly effective.

Example 3

R-1243zf has previously found use as a monomer and as an olefin mightreasonably be expected to be susceptible to polymerisation or otherreactions particularly when contacted with reactive surfaces present inmany of the absorbents used in the process of the invention. This wouldseriously limit the commercial applicability of this invention.Therefore, we sought to investigate whether any reaction processesaccompanied the adsorptive purification of R-1243zf by contacting withabsorbents such as ST1x carbon and AW500.

Samples of ST1x carbon and AW500 were pre-treated at 200-300° C. underflowing nitrogen for 16 hours prior to use. 20 g samples were then takenand accurately weighed and added to a clean, dry 300 ml Hastelloyautoclave either individually or together. The autoclave was sealed,purged with nitrogen and pressure tested. The autoclave was then chargedwith R-1243zf. The autoclave and its contents were then heated to either80 or 120° C. for a period of 24 hours. At the end of each experiment,the R-1243zf was recovered for analysis. The adsorbent was alsorecovered and following drying at 105° C. was re-weighed. The resultsare presented in the Tables below.

At the end of each experiment the recovered R-1243zf was visuallyunchanged. There were no residues left behind upon evaporation of theR-1243zf following each test. The detailed analysis revealed that theadsorbents ST1x and AW500 either alone or particularly in combinationwere still effective under the conditions of these tests. Furthermore,there was no evidence for any undesirable side reactions includingpolymerisation or decomposition. Therefore these adsorbents alone and incombination were shown to be suitable for the purification of e.g.R-1243zf at commercial scale.

Feed 1225ye- Impurity 227 ea 134a 1225zc 1234yf 134 Z 152a CH,CI Feed5.1747   2.1878 7.6842 27.7435 78.5234 0.8828 266.3725 0.8193 Impuritylevel ppm wt/wt Stability test-impurity levels post experiment AW 500 0— 4.7881 20.8933  9.3329 1.8548  58.2016 0 Molecular sieve @ 80 degautoclave ref. 65 AW 500 0  66.0333 8.4049 28.4736  9.4839 0.911 50.6359 0 Molecular sieve sieve @ 80 deg autoclave ref 66 AW 500 0107.839 6.3199 26.1201  9.6007 0.8829  35.9887 0 Molecular sieve @ 120deg autoclave ref 65 AW 500 0  38.5844 6.5352 27.1244  9.7792 0.6821 38.0479 0 Molecular sieve @ 120 deg autoclave ref 66 ST1X 0  93.6399 027.304 77.6009 0 250.1089 0 Carbon @ 80 deg autoclave ref 65 ST1X 0 43.5858 0 28.0388 78.8577 0 256.46 0 Carbon @ 80 deg autoclave ref 66ST1X 0  99.3595 0 25.7188 74.9626 0 239.8486 0 Carbon @ 120 degautoclave ref 65 ST1X 0  48.7522 0 27.7375 72.7737 0 242.8736 0 Carbon @120 deg autoclave ref 66 Mol sieve/ 0  47.5807 0 26.224 36.0314 0140.276 0 Carbon @ 80 deg autoclave ref 65 Mol sieve/ 0  38.0292 025.7825 35.3323 0 139.7663 0 Carbon @ 80 deg autoclave ref 66 Mol sieve/0  46.2215 0 26.1542 37.4035 0 145.5055 0 Carbon @ 120 deg autoclave ref65 Mol sieve/ 0  35.5752 0 26.5073 35.9233 0 149.4047 0 Carbon @ 120 degautoclave ref 66 Feed Impurity 1122 31 133a 32 125 12 263fb 23 Feed0.6197 10.6993 3.0693  0 0  0  0 0 Impurity level ppm wt/wt Stabilitytest-impurity levels post experiment AW 500 0  0 1.222 94.4952 5.345726.304 14.7591 Molecular sieve @ 80 deg autoclave ref. 65 AW 500 0 0 0 0.5372 0  0  0 3.5424 Molecular sieve sieve @ 80 deg autoclave ref 66AW 500 0 0 0  0 0  0  0 0 Molecular sieve @ 120 deg autoclave ref 65 AW500 0 0 0  0 0  0  0 0 Molecular sieve @ 120 deg autoclave ref 66 ST1X 00 0 24.9735 0  0  0 0 Carbon @ 80 deg autoclave ref 65 ST1X 0 0 017.8747 0  0  0 0 Carbon @ 80 deg autoclave ref 66 ST1X 0 0 0 19.3595 0 7.7045  0 0 Carbon @ 120 deg autoclave ref 65 ST1X 0 0 0 15.9942 017.7729  0 0 Carbon @ 120 deg autoclave ref 66 Mol sieve/ 0 0 0  1.86490  0  0 0 Carbon @ 80 deg autoclave ref 65 Mol sieve/ 0 0 0  1.0693 0  0 0 0 Carbon @ 80 deg autoclave ref 66 Mol sieve/ 0 0 0  0 0  4.7912  0 0Carbon @ 120 deg autoclave ref 65 Mol sieve/ 0 0 0  1.5667 0  0  0 0Carbon @ 120 deg autoclave ref 66

80 Deg C. 120 Deg C. Mass Mass Mass Mass material Change/ % Wt materialChange/ % Wt tested/g g Change tested/g g Change AW 500 20.0274 +0.20661.54 20.0975 −0.1143 −0.57 Molecular 20.081 +0.1498 1.94 20.0589 −0.0940−0.47 Sieve ST1X 20.0156 +0.3912 1.95 20.127 +0.6425 3.19 Carbon 20.0086+0.3562 1.78 20.0141 +0.8135 4.06 50/50 20.0225 +0.4457 2.22 20.0337−0.1499 −0.75 AW500/ 20.073 +0.4964 2.47 20.0511 +0.4672 2.33 ST1X

Example 4

The process of the invention was operated at commercial scale to removetrace impurities from a 180 kg batch of R-1243zf. An 85-litre adsorptionbed was charged with 19.5 kg ST1x carbon and 19.5 kg AW500 molecularsieve. The Rig was sealed and evacuated to remove air. The feed vessels(total volume 270-litres) were charged with c.a. 180 kg of commerciallyavailable R-1243zf. This material contained similar impurities atsimilar levels to those specified in Example 2.

The crude R-1243zf was then pumped from the feed vessels up through theadsorption bed and back into the feed vessels at ambient temperature.The R-1243zf charged was recirculated in this manner through theadsorption bed for a period of 5 hours. After which period the R-1243zfwas pumped to a receiver vessel where it could be recovered for storageand analysis. After analysis each 180 kg charge was split into 60 kgbatches. It was found that the adsorbent charge was capable ofprocessing at least 360 kg of R-1243zf. The analysis of three 60 kgbatches of R-1243zf processed in this manner are presented in the Tablebelow:

Impurity Level Impurity Level Impurity Level Impurity Level aftertreatment - after treatment - after treatment - before treatment Batch 1Batch 2 Batch 3 Impurity (ppm wt/wt) (ppm wt/wt) (ppm wt/wt) (ppm wt/wt)1225zc 22 ND ND ND 1234yf 24 29 26 30 134 77 ND 4.0 11 Z-1225ye 4.9 2.53.5 3.6 152a 246 1.1 6.7 18 40 3.1 ND ND ND 31 11 ND ND ND Total 1243zf99.959 99.992 99.986 99.991

I/We claim:
 1. A process for removing one or more undesired(hydro)fluoroalkyne compounds from a (hydro)fluoroalkene, the processcomprising contacting a composition comprising the (hydro)fluoroalkeneand one or more undesired (hydro)fluoroalkyne compounds with analuminium-containing adsorbent, activated carbon, or a mixture thereof,wherein the (hydro)fluoroalkene does not contain a ═CF2 moiety.
 2. Aprocess according to claim 1 wherein the (hydro)fluoroalkene is a C3-7(hydro)fluoroalkene.
 3. A process according to claim 2 wherein the C3-7(hydro)fluoroalkene is a hydrofluoropropene.
 4. A process according toclaim 3 wherein the hydrofluoropropene is a trifluoropropene or atetrafluoropropene.
 5. A process according to claim 4 wherein thetrifluoropropene is 3,3,3-trifluoropropene (R-1243zf).
 6. A processaccording to claim 4 wherein the tetrafluoropropene isE/Z-1,3,3,3-tetrafluoropropene (R-1234ze).
 7. A process according toclaim 4 wherein the tetrafluoropropene is 2,3,3,3-tetrafluoropropene(R-1234yf).
 8. A process according to claim 1 wherein the(hydro)fluoroalkyne is trifluoromethylacetylene (TFMA).
 9. A processaccording to claim 1 wherein the aluminium-containing adsorbent isporous and comprises alumina or aluminosilicate.
 10. A process accordingto claim 9 wherein the alumina comprises acidic functionality.
 11. Aprocess according to claim 9 wherein the aluminosilicate is a molecularsieve (zeolite) having pore sizes in the range 3 to 12 Angstroms.
 12. Aprocess according to claim 1 wherein the activated carbon is impregnatedwith an additive selected from a metal, a metal compound, a base and amixture thereof.
 13. A process according to claim 12 wherein theadditive is an alkali metal salt.
 14. A process according to claim 1wherein the activated carbon has a surface area of from 50 to 3000 m2.15. A process according to claim 14 wherein the activated carbon has asurface area of from 100 to 2000 m2.
 16. A process according to claim 1wherein the or each undesired (hydro)fluoroalkyne compound is present inan amount of from about 0.1 to about 1000 ppm, based on the weight ofthe composition comprising the (hydro)fluoroalkene and one or moreundesired (hydro)fluoroalkyne compounds.
 17. A process according toclaim 16 wherein the or each undesired (hydro)fluoroalkyne compound ispresent in an amount of from 0.1 to 500 ppm.
 18. A process according toclaim 17 wherein the or each undesired (hydro)fluoroalkyne compound ispresent in an amount of from 1 to 100 ppm.
 19. A process according toclaim 1 wherein at least 50% of the or each undesired(hydro)fluoroalkyne compound present in the composition is removedtherefrom.
 20. A process according to claim 19 wherein at least 70% ofthe or each undesired (hydro)fluoroalkyne compound present in thecomposition is removed therefrom.
 21. A process according to claim 20wherein at least 90% of the or each undesired (hydro)fluoroalkynecompound present in the composition is removed therefrom.
 22. A processaccording to claim 1, wherein the process is conducted at from −50° C.to 200° C.
 23. A process according to claim 22, wherein the process isconducted at from 0° C. to 100° C.
 24. A process according to claim 23,wherein the process is conducted at from 10° C. to 50° C.
 25. A processaccording to claim 1 wherein following the contacting step, theresulting composition comprises the (hydro)fluoroalkene and from 0 to 10ppm of the or each undesired (hydro)fluoroalkyne compound.
 26. A processaccording to claim 25 wherein following the contacting step, theresulting composition comprises the (hydro)fluoroalkene and from 0 to 5ppm of the or each undesired (hydro)fluoroalkyne compound.
 27. A processaccording to claim 1 wherein the composition comprising the(hydro)fluoroalkene and one or more undesired (hydro)fluoroalkynecompounds is a product stream from a process for producing the(hydro)fluoroalkene.
 28. A process for removing one or more undesired(hydro)fluoroalkyne compounds from a (hydro)fluoroalkene according toclaim 27, which process is combined with one or more additionalpurification steps.